Polyethylene powder and method for producing same, and catalyst for olefin polymerization and method for producing same

Abstract

A polyethylene powderhaving a viscosity-average molecular weight of 100,000 or larger and 4,000,000 or smaller, andhaving a crystal thickness parameter of 5° C. or higher and 9° C. or lower obtained from measurement using a differential scanning calorimeter (DSC).

1 : A polyethylene powder
 having a viscosity-average molecular weight of 100,000 or larger and 4,000,000 or smaller, and   having a crystal thickness parameter of 5° C. or higher and 9° C. or lower obtained from measurement using a differential scanning calorimeter (DSC).   
     
     
         2 : The polyethylene powder according to  claim 1 , wherein a value of z-average shrinkage factor g z  measured using a gel permeation chromatography (GPC) measurement apparatus combined with a differential refractometer and a viscosity detector is 0.600 or more and 1 or less. 
     
     
         3 : The polyethylene powder according to  claim 1 , wherein a peak top temperature (Tm2 top ) in a DSC curve of a second heating process obtained by measurement shown in the following <Measurement conditions> using a differential scanning calorimeter (DSC) is 135° C. or higher and 140° C. or lower:
 <Measurement conditions> 
 (1) left standing at 50° C. for 1 min, 
 (2) heated from 50° C. to 180° C. at 10° C./min (first heating process), 
 (3) left standing at 180° C. for 5 min, 
 (4) cooled from 180° C. to 50° C. at 10° C./min, 
 (5) left standing at 50° C. for 5 min, and 
 (6) heated from 50° C. to 180° C. at 10° C./min (second heating process), and
 the crystal thickness parameter is 6.7° C. or higher and 9.0° C. or lower. 
 
 
     
     
         4 : The polyethylene powder according to  claim 2 , wherein the polyethylene powder is drawable under the following conditions:
 (Drawing conditions)   a 100 mm×100 mm×1 mm thick gel sheet made of 30% by mass of the polyethylene powder and 70% by mass of liquid paraffin is drawn at a ratio of 7×7 at 115° C.   
     
     
         5 : The polyethylene powder according to  claim 2 , wherein an absorption coefficient at 400 cm −1  to 450 cm −1  in terahertz measurement is 1.0 or more and 4.0 or less. 
     
     
         6 : The polyethylene powder according to  claim 2 , wherein no peak is present in the following regions in  1 H-NMR measurement:
 (1) 4.8 ppm to 5.0 ppm, and   (2) 5.6 ppm to 6.0 ppm.   
     
     
         7 : The polyethylene powder according to  claim 2 , wherein an aluminum content is 0 ppm or more and 50 ppm or less. 
     
     
         8 : The polyethylene powder according to  claim 2 , wherein a silicon content is 0 ppm or more and 30 ppm or less. 
     
     
         9 : The polyethylene powder according to  claim 2 , wherein a peak top temperature in a DSC curve of a second heating process in differential scanning calorimeter (DSC) measurement is 130° C. or higher and 140° C. or lower. 
     
     
         10 : The polyethylene powder according to  claim 2 , wherein a density is 920 kg/m 3  or more and 960 kg/m 3  or less. 
     
     
         11 : The polyethylene powder according to  claim 2  for a battery separator. 
     
     
         12 : A method for producing a catalyst for olefin polymerization, comprising:
 a first supporting reaction step of reacting a solid particle [A] with a transition metal compound component [B-1] and/or a transition metal compound component [B-2] and an activating agent [C] and/or an organic metal compound component [D]; and   a second supporting reaction step of reacting the particle obtained in the first supporting reaction step with the transition metal compound component [B-1] and/or the transition metal compound component [B-2] and the activating agent [C] and/or the organic metal compound component [D], wherein   the transition metal compound component [B-1] is a compound represented by the following (Formula 3), the transition metal compound component [B-2] is a compound represented by the following (Formula 4), the activating agent [C] is a compound represented by the following (Formula 5) or (Formula 6), the organic metal compound component [D] is a compound containing at least one metal selected from the group consisting of group 1, group 2, group 12, and group 13 of the periodic table, and the solid particle [A] is a porous polymer material or an inorganic solid particle containing at least one element selected from the group consisting of group 2 to group 4, group 13, and group 14 of the periodic table, and   the following <Condition 1> and/or <Condition 2> is satisfied:   
       <Condition 1>
 the first supporting reaction step comprises: a premixing step of reacting the transition metal compound component [B-1] and/or the transition metal compound component [B-2] with the activating agent [C] and/or the organic metal compound component [D]; and the step of reacting the solid particle [A] with the mixture obtained in the premixing step, 
 
       <Condition 2>
 in the first supporting reaction step, a molar ratio (([C]+[D])/[B]) of a molar quantity ([C]+[D]) of the activating agent [C] and the organic metal compound component [D] to a molar quantity [B] of the transition metal compound component [B-1] and/or the transition metal compound component [B-2] is 1 or more and 60 or less,
   L 1   j W k M 1 X 1   p X 2   q   (Formula 3)
 
 
 
       wherein
 each L 1  independently represents a η-binding cyclic anion ligand selected from the group consisting of a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, a tetrahydrofluorenyl group, and an octahydrofluorenyl group, and the ligand optionally has 1 to 8 substituents, wherein the substituents are each independently a substituent having up to 20 non-hydrogen atoms selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-substituted hydrocarbon group having 1 to 12 carbon atoms, an aminohydrocarbyl group having 1 to 12 carbon atoms, a hydrocarbyloxy group having 1 to 12 carbon atoms, a dihydrocarbylamino group having 1 to 12 carbon atoms, a hydrocarbylphosphino group having 1 to 12 carbon atoms, a silyl group, an aminosilyl group, a hydrocarbyloxysilyl group having 1 to 12 carbon atoms, and a halosilyl group, 
 M 1  is a transition metal with a formal oxidation number of +2, +3, or +4 selected from a transition metal group belonging to group 4 of the periodic table and represents a transition metal η5-bonded to at least one ligand L 1 , 
 W is a divalent substituent having up to 50 non-hydrogen atoms and represents a divalent substituent that is bonded to L 1  and M 1  with respective valences of 1, thereby forming a metallocycle in cooperation with L 1  and M 1 , 
 each X 1  independently represents an anionic σ-binding ligand having up to 60 non-hydrogen atoms selected from the group consisting of a monovalent anionic σ-binding ligand, a divalent anionic σ-binding ligand bonded to M 1  with divalence, and a divalent anionic σ-binding ligand bonded to L 1  and M 1  with respective valences of 1, 
 each X 2  independently represents a neutral Lewis base-coordinating compound having up to 40 non-hydrogen atoms, 
 j is 1 or 2, provided that when j is 2, two ligands L 1  are optionally bonded to each other via a divalent group having up to 20 non-hydrogen atoms, wherein the divalent group is a group selected from the group consisting of a hydrocarbadiyl group having 1 to 20 carbon atoms, a halohydrocarbadiyl group having 1 to 12 carbon atoms, a hydrocarbyleneoxy group having 1 to 12 carbon atoms, a hydrocarbyleneamino group having 1 to 12 carbon atoms, a silanediyl group, a halosilanediyl group, and a silyleneamino group, k is 0 or 1, p is 0, 1, or 2, provided that when X 1  is a monovalent anionic σ-binding ligand, or a divalent anionic σ-binding ligand bonded to L 1  and M 1 , p is an integer smaller by 1 or more than the formal oxidation number of M 1 , when X 1  is a divalent anionic σ-binding ligand bonded only to M 1 , p is an integer smaller by (j+1) or more than the formal oxidation number of M 1 , and q is 0, 1, or 2, 
 
       
         
           
           
               
               
           
         
       
       wherein
 M 2  is a transition metal selected from the group consisting of titanium, zirconium, and hafnium and represents a transition metal with a formal oxidation number of +2, +3, or +4, 
 each R 5  independently represents a hydrogen atom or a substituent having 1 to 20 non-hydrogen atoms selected from the group consisting of a hydrocarbon group having 1 to 8 carbon atoms, a silyl group, a germyl group, a cyano group, a halogen atom, and a complex group thereof, provided that when the substituent R 5  is a hydrocarbon group having 1 to 8 carbon atoms, a silyl group, or a germyl group, two adjacent substituents R 5  are optionally bonded to each other to form a divalent group, thereby forming a ring in cooperation with a bond between two carbon atoms of a cyclopentadienyl ring bonded to the two adjacent substituents R 5 , respectively, 
 each X 3  independently represents a substituent having 1 to 20 non-hydrogen atoms selected from the group consisting of halide, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 18 carbon atoms, a hydrocarbylamino group having 1 to 18 carbon atoms, a silyl group, a hydrocarbylamide group having 1 to 18 carbon atoms, a hydrocarbyl phosphide group having 1 to 18 carbon atoms, a hydrocarbyl sulfide group having 1 to 18 carbon atoms, and a complex group thereof, provided that two substituents X 3  optionally form neutral conjugated diene or a divalent group having 4 to 30 carbon atoms in cooperation, 
 Y 1  represents —O—, —S—, —NR 6 —, or —PR 6 —, wherein R 6  represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, a hydrocarbyloxy group having 1 to 8 carbon atoms, a silyl group, an alkyl halide group having 1 to 8 carbon atoms, an aryl halide group having 6 to 20 carbon atoms, or a complex group thereof, 
 Z 1  represents SiR 6   2 , CR 6   2 , SiR 6   2 SiR 6   2 , CR 6   2 CR 6   2 , CR 6 ═CR 6 , CR 6   2 SiR 6   2 , or GeR 6   2 , wherein R 6  is as defined above, and 
 n is 1, 2, or 3,
   (C-1):[L 2 -H] d+ [M 3   r Q s ] d−   (Formula 5)
 
 
 wherein [L 2 -H] d+  is a proton-donating Bronsted acid, L 2  is a neutral Lewis base; [M 3   r Q s ] d−  in the formula is a compatible non-coordinating anion, M 3  is a metal or a metalloid selected from group 5 to group 15 of the periodic table, each Q is independently hydride, a dialkylamide group, halide, an alkoxide group, an allyloxide group, a hydrocarbon group, or a substituted hydrocarbon group having up to 20 carbon atoms, and the number of halides Q is 1 or less; r is an integer of 1 to 7, s is an integer of 2 to 14, d is an integer of 1 to 7, and s−r=d,
   (C-2):-(M 4 R 7   t-2 —O) u —  (Formula 6)
 
 
 wherein M 4  is a metal or a metalloid of group 13 to group 15 of the periodic table, each R 7  is independently a hydrocarbon group or a substituted hydrocarbon group having 1 to 12 carbon atoms, t is the valence of the metal M 4 , and u is an integer of 2 or larger. 
 
     
     
         13 : The method for producing a catalyst for olefin polymerization according to  claim 12 , wherein the solid particle [A] is a magnesium chloride particle. 
     
     
         14 : A catalyst for olefin polymerization, comprising
 a solid particle [A], a transition metal compound component [B-1] and/or a transition metal compound component [B-2], and an activating agent [C] and/or an organic metal compound component [D], wherein   the transition metal compound component [B-1] is a compound represented by the following (Formula 3), the transition metal compound component [B-2] is a compound represented by the following (Formula 4), the activating agent [C] is a compound represented by the following (Formula 5) or (Formula 6), the organic metal compound component [D] is a compound containing at least one metal selected from the group consisting of group 1, group 2, group 12, and group 13 of the periodic table, and the solid particle [A] is a porous polymer material or an inorganic solid particle containing at least one element selected from the group consisting of group 2 to group 4, group 13, and group 14 of the periodic table,   a content (mol) of a central metal M contained in the transition metal compound component [B-1] and/or the transition metal compound component [B-2] is 20 μmol or more and 1000 μmol or less, and a molar ratio (AI/M) of a content (mol) of Al to the content (mol) of the central metal M is 1 or more and 30 or less:
   L 1   j W k M 1 X 1   p X 2   q   (Formula 3)
 
   
       wherein
 each L 1  independently represents a η-binding cyclic anion ligand selected from the group consisting of a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, a tetrahydrofluorenyl group, and an octahydrofluorenyl group, and the ligand optionally has 1 to 8 substituents, wherein the substituents are each independently a substituent having up to 20 non-hydrogen atoms selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-substituted hydrocarbon group having 1 to 12 carbon atoms, an aminohydrocarbyl group having 1 to 12 carbon atoms, a hydrocarbyloxy group having 1 to 12 carbon atoms, a dihydrocarbylamino group having 1 to 12 carbon atoms, a hydrocarbylphosphino group having 1 to 12 carbon atoms, a silyl group, an aminosilyl group, a hydrocarbyloxysilyl group having 1 to 12 carbon atoms, and a halosilyl group, 
 M 1  is a transition metal with a formal oxidation number of +2, +3 or +4 selected from a transition metal group belonging to group 4 of the periodic table and represents a transition metal η5-bonded to at least one ligand L 1 , 
 W is a divalent substituent having up to 50 non-hydrogen atoms and represents a divalent substituent that is bonded to L 1  and M 1  with respective valences of 1, thereby forming a metallocycle in cooperation with L 1  and M 1 , 
 each X 1  independently represents an anionic σ-binding ligand having up to 60 non-hydrogen atoms selected from the group consisting of a monovalent anionic σ-binding ligand, a divalent anionic σ-binding ligand bonded to M 1  with divalence, and a divalent anionic σ-binding ligand bonded to L 1  and M 1  with respective valences of 1, 
 each X 2  independently represents a neutral Lewis base-coordinating compound having up to 40 non-hydrogen atoms, 
 j is 1 or 2, provided that when j is 2, two ligands L 1  are optionally bonded to each other via a divalent group having up to 20 non-hydrogen atoms, wherein the divalent group is a group selected from the group consisting of a hydrocarbadiyl group having 1 to 20 carbon atoms, a halohydrocarbadiyl group having 1 to 12 carbon atoms, a hydrocarbyleneoxy group having 1 to 12 carbon atoms, a hydrocarbyleneamino group having 1 to 12 carbon atoms, a silanediyl group, a halosilanediyl group, and a silyleneamino group, k is 0 or 1, p is 0, 1, or 2, provided that when X 1  is a monovalent anionic σ-binding ligand, or a divalent anionic σ-binding ligand bonded to L 1  and M 1 , p is an integer smaller by 1 or more than the formal oxidation number of M 1 , when X 1  is a divalent anionic σ-binding ligand bonded only to M 1 , p is an integer smaller by (j+1) or more than the formal oxidation number of M 1 , and q is 0, 1, or 2, 
 
       
         
           
           
               
               
           
         
       
       wherein
 M 2  is a transition metal selected from the group consisting of titanium, zirconium, and hafnium and represents a transition metal with a formal oxidation number of +2, +3, or +4, 
 each R 5  independently represents a hydrogen atom or a substituent having 1 to 20 non-hydrogen atoms selected from the group consisting of a hydrocarbon group having 1 to 8 carbon atoms, a silyl group, a germyl group, a cyano group, a halogen atom, and a complex group thereof, provided that when the substituent R 5  is a hydrocarbon group having 1 to 8 carbon atoms, a silyl group, or a germyl group, two adjacent substituents R 5  are optionally bonded to each other to form a divalent group, thereby forming a ring in cooperation with a bond between two carbon atoms of a cyclopentadienyl ring bonded to the two adjacent substituents R 5 , respectively, 
 each X 3  independently represents a substituent having 1 to 20 non-hydrogen atoms selected from the group consisting of halide, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 18 carbon atoms, a hydrocarbylamino group having 1 to 18 carbon atoms, a silyl group, a hydrocarbylamide group having 1 to 18 carbon atoms, a hydrocarbyl phosphide group having 1 to 18 carbon atoms, a hydrocarbyl sulfide group having 1 to 18 carbon atoms, and a complex group thereof, provided that two substituents X 3  optionally form neutral conjugated diene or a divalent group having 4 to 30 carbon atoms in cooperation, 
 Y 1  represents —O—, —S—, —NR 6 —, or —PR 6 —, wherein R 6  represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, a hydrocarbyloxy group having 1 to 8 carbon atoms, a silyl group, an alkyl halide group having 1 to 8 carbon atoms, an aryl halide group having 6 to 20 carbon atoms, or a complex group thereof, 
 Z 1  represents SiR 6   2 , CR 6   2 , SiR 6   2 SiR 6   2 , CR 6   2 CR 6   2 , CR 6 ═CR 6 , CR 6   2 SiR 6   2 , or GeR 6   2 , wherein R 6  is as defined above, and 
 n is 1, 2, or 3,
   (C-1):[L 2 -H] d+ [M 3   r Q s ] d−   (Formula 5)
 
 
 wherein [L 2 -H] d+  is a proton-donating Bronsted acid, L 2  is a neutral Lewis base; [M 3   r Q s ] d−  in the formula is a compatible non-coordinating anion, M 3  is a metal or a metalloid selected from group 5 to group 15 of the periodic table, each Q is independently hydride, a dialkylamide group, halide, an alkoxide group, an allyloxide group, a hydrocarbon group, or a substituted hydrocarbon group having up to 20 carbon atoms, and the number of halides Q is 1 or less; r is an integer of 1 to 7, s is an integer of 2 to 14, d is an integer of 1 to 7, and s−r=d,
   (C-2):-(M 4 R 7   t-2 —O) u —  (Formula 6)
 
 
 wherein M 4  is a metal or a metalloid of group 13 to group 15 of the periodic table, each R 7  is independently a hydrocarbon group or a substituted hydrocarbon group having 1 to 12 carbon atoms, t is the valence of the metal M 4 , and u is an integer of 2 or larger. 
 
     
     
         15 : The catalyst for olefin polymerization according to  claim 14 , wherein the solid particle [A] is a magnesium chloride particle. 
     
     
         16 : A method for producing an olefin polymer, comprising the step of polymerizing olefin using the catalyst for olefin polymerization according to  claim 14 . 
     
     
         17 : The polyethylene powder according to  claim 3 , wherein the polyethylene powder is drawable under the following conditions:
 (Drawing conditions)
 a 100 mm×100 mm×1 mm thick gel sheet made of 30% by mass of the polyethylene powder and 70% by mass of liquid paraffin is drawn at a ratio of 7×7 at 115° C. 
   
     
     
         18 : The polyethylene powder according to  claim 3 , wherein an absorption coefficient at 400 cm −1  to 450 cm −1  in terahertz measurement is 1.0 or more and 4.0 or less. 
     
     
         19 : The polyethylene powder according to  claim 3 , wherein no peak is present in the following regions in  1 H-NMR measurement:
 (1) 4.8 ppm to 5.0 ppm, and   (2) 5.6 ppm to 6.0 ppm.   
     
     
         20 : The polyethylene powder according to  claim 3 , wherein an aluminum content is 0 ppm or more and 50 ppm or less.